CN101142020B - Catalyst for producing carbon nanotubes by decomposing gaseous carbon compounds on heterogeneous catalysts - Google Patents

Catalyst for producing carbon nanotubes by decomposing gaseous carbon compounds on heterogeneous catalysts Download PDF

Info

Publication number
CN101142020B
CN101142020B CN200580046507XA CN200580046507A CN101142020B CN 101142020 B CN101142020 B CN 101142020B CN 200580046507X A CN200580046507X A CN 200580046507XA CN 200580046507 A CN200580046507 A CN 200580046507A CN 101142020 B CN101142020 B CN 101142020B
Authority
CN
China
Prior art keywords
catalyst
solution
deionized water
cnt
minutes
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN200580046507XA
Other languages
Chinese (zh)
Other versions
CN101142020A (en
Inventor
S·布克霍尔茨
D·G·杜夫
V·米彻尔
L·穆尔克兹科
C·穆尼克
R·鲁多夫
A·沃夫
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Bayer Intellectual Property GmbH
Original Assignee
Bayer MaterialScience AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer MaterialScience AG filed Critical Bayer MaterialScience AG
Publication of CN101142020A publication Critical patent/CN101142020A/en
Application granted granted Critical
Publication of CN101142020B publication Critical patent/CN101142020B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials
    • C01B32/158Carbon nanotubes
    • C01B32/16Preparation
    • C01B32/162Preparation characterised by catalysts
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/10Magnesium; Oxides or hydroxides thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889Manganese, technetium or rhenium
    • B01J23/8892Manganese
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889Manganese, technetium or rhenium
    • B01J23/8898Manganese, technetium or rhenium containing also molybdenum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82BNANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B82B3/0004Apparatus specially adapted for the manufacture or treatment of nanostructural devices or systems or methods for manufacturing the same
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/127Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/221Carbon nanotubes
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60Organic compounds having low molecular weight
    • H10K85/615Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00Structure or properties of carbon nanotubes
    • C01B2202/20Nanotubes characterized by their properties
    • C01B2202/34Length
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00Structure or properties of carbon nanotubes
    • C01B2202/20Nanotubes characterized by their properties
    • C01B2202/36Diameter

Abstract

The invention relates to a method for producing carbon nanotubes, in particular carbon nanotubes having a diameter of 3 to 150nm and an aspect ratio of length to diameter (L: D) of >100, by decomposing hydrocarbons over a heterogeneous catalyst comprising Mn, Co, preferably also molybdenum, and an inert support material, and to the catalyst and the carbon nanotubes themselves and to the use thereof.

Description

Be used for through on heterogeneous catalysis, decomposing the catalyst that gaseous carbon compound prepares CNT
The present invention relates to a kind of through comprising Mn, Co; Preferably also comprise molybdenum; And decompose hydrocarbon on the heterogeneous catalysis of inert support material and prepare CNT, particularly diameter is 3-150nm and length: diameter (L: aspect ratio D)>method and the said catalyst and CNT itself and application thereof of 100 CNT.
CNT mainly be meant diameter between 3-80nm and length be the several times of diameter, at least 100 times cylindrical carbon spermaduct.These pipes are made up of orderly carbon atomic layer and have a core that form is different.These CNTs for example also are known as " carbon fibrils " or " hollow carbon fiber ".Because its size and property thereof, said CNT are extremely important for making composite in industry.Main further application also comprises electronics, the energy and other field.
This material of CNT is known to have had the long period.Although claim the finder (S.Iijima, Nature354,56-58,1991) that Iijima in 1991 is a nanotube usually, the fibrous graphite material that these materials particularly have a plurality of graphite linings is the known long period already.For example recorded and narrated through the superfine fibrous carbon of catalytic decomposition hydrocarbon deposition (GB1469930A1,1977, and EP56004A2,1982, Tates and Baker) the seventies and the early stage people of the eighties.However, based on the further characteristic of the carbon filament of short hydrocarbon manufacturing and do not lie in its diameter.Especially in EP205556B1 and WO86/03455A, also recorded and narrated the preparation of diameter less than the CNT of 100nm.Wherein recorded and narrated the lighter hydrocarbons that are used for said preparation (be short chain or medium chain aliphatic hydrocarbon, or list or double ring arene) and ferrum-based catalyst, carbon carrier is decomposing in the temperature more than 800-900 ℃ on the above-mentioned ferrum-based catalyst.Known method comprises for example electric arc, laser ablation and catalysis method.Manyly in these methods all can form carbon black, amorphous carbon and large diameter fiber as byproduct.In catalysis method, can distinguish in the deposition on the catalyst granules of load and form in position and diameter is the deposition (so-called assembly line method) on the nano level metal center.Through by (being called CCVD hereinafter for the hydrocarbon catalytic deposition carbon of gaseous state under the reaction condition; The catalyzed carbon gas deposition) under the situation of making, possible carbon has acetylene, methane, ethane, ethene, butane, butylene, butadiene, benzene and other carbon raw material to body.Catalyst generally includes metal, metal oxide and maybe can decompose or reducible metal component.For example, in the prior art metal species Fe, Mo, Ni, V, Mn, Sn, Co, Cu etc. are arranged.Though single metal usually has the tendency that forms nanotube, advantageously the metallic catalyst of the combination through containing above-mentioned metal is realized according to prior art high yield and low agraphitic carbon content.According to prior art, preferred especially system is based on the combination that contains Fe or Ni.The formation of CNT and the characteristic of formed CNT depend on fusion, reaction temperature, the time of staying and reactor used as interaction, unstrpped gas and dividing potential drop thereof, hydrogen or other gas between combination, used carrier material and the catalyst and the carrier of the metal component of catalyst or multiple metal component with a kind of very complicated mode.Being optimized for industrial process is a very big difficult problem.
It should be noted that the metal component that is used for CCVD and is known as catalyst is consumed in the process of this synthesis technique.This consumption should for example cause particle to be covered (those skilled in the art are referred to as " Encapping ") fully because carbon is deposited on owing to the inactivation of metal component on the whole particle.Activation is normally impossible or infeasible economically again.Often every gram catalyst can only obtain a few gram CNTs at most, and said catalyst comprises used whole carrier and catalyst.Because the consumption of said catalyst, be a basic demand to catalyst and technology based on the high yield of the CNT of the catalyst meter that is adopted.
For the commercial production CNT; For example as improving the mechanical performance of composite or the component of electric conductivity; As all industrial process, all to pursue high spatial/time productive rate, keep the ins and outs of nanotube simultaneously and used energy and operative material are minimized.Application based on the laser ablation of carbon often can only provide low-yield and high amorphous carbon or content of carbon black.These structures have only the laboratory scale of several grams every day to be difficult to usually realize to plant-scale conversion from productive rate.Therefore, laser ablation is equally very expensive and be difficult to enlargement of scale.Though the various methods of in document, being recorded and narrated through CCVD manufacturing CNT also seem very low productivity ratio is often only arranged bases fit for various catalyst.Also recorded and narrated catalyst and specific reactions stage used when making CNT in the document, these specific reactions stages except that the stage of reaction that deposits have also described in specific reactions atmosphere like the target preliminary treatment in the reductive hydrogen atmosphere especially.
Use below from various documents particularly the following example of patent documentation and the list of references that comprises thereof prior art is described.
Known preparation for CNT has the whole bag of tricks and catalyst.In EP0205556A1 (Hyperion Catalysis International), recorded and narrated this CNT.A kind of catalyst and the reaction of various hydrocarbon under high temperature more than 800-1000 ℃ of iron content recorded and narrated in this protection power application of being quoted.Use Ni as catalyst equally also at for example M.G.Nijkamp; Universiteit Utrecht; NL has record in 2002 the paper " Hydrogen Storageusing Physisorption Modified Carbon Nanofibers and RelatedMaterials ".People such as Shaikhutdinov (Shamil ' K.Shaikhutdinov, L.B.Avdeeva, O.V.Goncharova; D.I.Kochubey; B.N.Novgorodov, L.M.Plyasova, " Coprecipitated Ni-Al and Ni-Cu-Al catalysts formethane decomposition and carbon deposition I. "; Applied CatalysisA:General; 126,1995,125-139 page or leaf) having recorded and narrated the Ni matrix equally ties up to methane decomposition and prepares in the carbon nanomaterial as active material.For example Geus and DeJong have provided the further summary about manufacturing approach in one piece of summary property paper (K.P.De Jong and J.W.Geus, Catal.Rev.-Sci.Eng.42 (4), 2000,481-510 page or leaf).WO03/004410 (Nanocyl) for example, US6358878B1 (Hyperion CatalysisInternational), US6518218B1 (general electronic corporation), disclosed among the CN1443708 (Zhejiang University), the combination of simple metal and various metals also can be used.Yet the optimum point of production of carbon tube is always not satisfactory usually, perhaps must pay higher industry expenditure for the material that obtains to have desired characteristic, is explained as follows.The commercial production of CNT is the theme of many researchs.Save the importance of described catalyst for the preparation of CNT according to this, the final response of used reaction unit and catalyst system therefor and prepared nano material is closely bound up.Though also can adopt similar catalytic activity element or its combination, the optimum condition of industrial reaction step only just can manifest in the complicacy interaction of the hydrodynamics in unstrpped gas and concentration, specificity of catalyst, reactor and properties of product.
EP1375424A1 has recorded and narrated a kind of industrial device that is used to prepare carbon nanomaterial, has also mentioned a kind of very general catalyst composition.Said catalyst exists Fe, Ni or Co element in forming.But and not mentioned any definite, particularly suitable composition.In people's such as Cassell a works, recorded and narrated and be used to prepare that the various iron of SWCN/the molybdenum system is catalyst based.Use the 5g catalyst, only can make 1.5g CNT (Cassell etc., " Large ScaleSynthesis of Single-Walled Carbon Nanotubes ", Journal of PhysicalChemistry, 1999,103 (31), 6484-6492 page or leaf).People such as Wang (Y.Wang; F.Wie, G.Gu and H.Yu, " Agglomerated carbon nanotubes and its massproduction in a fluidized bed reactor "; Physica B; 2002,323,327-329 page or leaf) recorded and narrated pure Fe catalyst has been used for the preparation less than the aggregation of 100 μ m.Porous material (silica for example; Aluminium oxide or zeolite) use can cause observing more carbon black and/or amorphous carbon forms and these carrier materials because its chemical resistance is difficult to the shortcoming (Hiura etc. that do not purified and from material with carbon element, separate caustically; NEC Corporation, US5698175).
For the catalytic component in the purifying carbon nanometre tube, can adopt and for example use alkali inorganic acid dilution or the hyperoxia voltinism, dilution or that concentrate or purifying step (K.Hernadi etc., the Solid State Ionincs of their combination; 141-142,2001,203-209; M.Toebes etc., Catalysis, 42; 2004,307-315).
EP 1318102A1 and WO 03/004410 A1 (Nanocyl S.A.) have put down in writing based on the catalyst that is positioned at Fe on the especially selected carrier, Co, Ni, V, Mo, Cu element.Its maximum yield value always is m Nanotube/ m Catalyst≤5-6.Selected carrier should be easy to purify and prepared nanotube has useful characteristic.Hydroxide and carbonate are used as concrete carrier, but such as one of ordinary skill in the art knowledge, they can be converted to corresponding oxide under the required temperature of synthesize nano carbon material.In addition, these carriers also must prepare respectively, and apply the active component of being made up of one or more metal oxide or reducible metallic compound to these carriers.Here, the amount of the active component that can apply is limited, because have only the active component of low load could produce polymolecularity and little primary particles diameter; Just make the formation of CNT become possible (G.Ertl thus;
Figure S05846507X20070716D000041
J.Weitkamp, Handbook Of HeterogeneousCatalysis, VCH; Weinheim; Germany, 1997, vol.Below 1,191 page, K.P.De Jong, J.W.Geus, Catal.Rev.Sci.Eng., 2000,42,4,481-510, the paper of M.S.Hoogenraad, Universiteit Utrecht, NL, 1995).
EPl368505 A1 (Electrovac) has recorded and narrated with Ni base or the catalyst based coated substrate of Co.About this point, preparation has the Ni that do not use electric current deposition or the base material of the catalyst based certain layer of Co needs very high producing cost.And the catalyst in this can only batch operation technology will stand the hot activation stage in reducing atmosphere, and this means extra spending again.
WO200006311 A1 has recorded and narrated a kind of technology for preparing nano-tube film, and catalyst wherein can comprise Fe, Co, Al, Ni, Mn, Pd, Cr and composition thereof.Yet, wherein catalyst is not further described, any specific appropriate combination of not mentioned these elements yet.
US2003/0148097 A1 has recorded and narrated a kind of method for preparing the nanotube of spirality or distortion, and wherein catalyst can influence the form of product.Its catalyst comprises one or more element that is selected from Fe, Co, Al, Ni, Mn, Pd and Cr or the combination of these elements or its mixture and other element or oxide.But and any particular combination of the not mentioned element of gathering since then for coming of improving that productive rate selects.
It is said and to obtain to have outstanding particularly the optimizing structure of dispersibility of characteristic of mixing through specific carrier/constitution.Especially the structure of carbon nanomaterial is optimized in this way.For manufacturing is exclusively used in the specific variants of the CNT of polymer, US6 for example, 358, (Hyperion Catalysis International Inc.) also reported and used the carrier with abundant limiting structure among the 878B1.Long nanotube and fiber arrange to be to have through use to the partial parallel of bundle and can to split the flat surfaces structure or carrier material that this crystallite that splits the surface forms realizes by just in time having.Though these materials can produce the material that is particularly suitable for polymer applications, active component preferably applies through immersion and impregnation technology.But known in the document like the preparation heterogeneous catalysis, the catalyst loadings that has polymolecularity simultaneously is limited.Certainly, the high dispersiveness of active catalyst component or minor diameter are favourable for the growth of CNT.Little active component diameter can only could be realized under low load capacity and polymolecularity when flooding or being deposited on the catalyst carrier.Therefore, the usefulness of catalyst system therefor is severely limited.US6,358, the 20-25 that it is catalyst system therefor weight that 878B1 mentions typical productive rate magnitude is doubly.Unexposed higher productive rate.Use said catalyst, before further using, must these residues be removed to such an extent as to the content of catalyst and carrier residue is also very high.This will cause producing cost to raise, and it relates to a plurality of other operations.And the form of CNT and characteristic can be put in order based on selected technology mode and purification influences under certain conditions.
It for example also is the target among the above-mentioned application WO03/004410A1 that catalyst is easy to remove.The hydroxide that uses Ca, Mg, Al, Ce, Ti, La and/or carbonate have been mentioned as carrier as this way to solve the problem.
Substantially, the problem of known technology of prior art and catalyst is that catalytic amount is unsatisfactory with the ratio of prepared CNT amount.
The objective of the invention is to develop on the basis of existing technology a kind of be used to the make catalyst and the technology of CNT as stated now; It makes can be with industrial effective and efficient manner, and promptly high especially as far as possible feed stock conversion and low catalyst addition are made diameter 3-200nm; 3-150nm preferably; Particularly preferably 3-60nm and aspect ratio L: D>100, preferably>500,3000 multilayer carbon nanotube particularly preferably >.
The present invention therefore provide a kind of catalyst with use this catalyst on heterogeneous catalysis by vapour deposition CNT technology; The basic components of wherein said heterogeneous catalysis is Mn and Co; Preferred Mn is similar ratio with Co; Preferably also there is Mo and randomly has other transition metal, be employed under the reaction condition hydrocarbon for gaseous state as raw material.
In the experiment of heterogeneous catalysis deposition of carbon nanotubes; The unexpected discovery can not only produce CNT with fine quality and high content of graphite based on the catalyst of element M n-Co; Then and the productive rate of CNT, based on the weight meter of catalyst system therefor, also high especially under the reaction condition that is fit to.Obtained than the Fe and the higher productive rate of Fe/Mo catalyst that use preparation in a similar manner unexpectedly.
About this point, CNT is all of a sudden with the form growth of " expanding universe ", and the catalyst primary particles that is included in the catalyst aggregation is separated and organizator density by the nanotube of all directions growth in the statistics upper edge<500kgm -3more loose material.
Catalyst according to the invention is based on manganese and cobalt component.It is favourable adding molybdenum.Except that basic components, also can add one or more metal component.The latter's example comprises all transition metal, is preferably based on the metal component of element of Fe, Ni, Cu, W, V, Cr, Sn.Catalyst according to the invention preferably comprises the Mn of 2-98mol% and the Co of 2-98mol% based on the active component composition meter of metallic forms.Especially preferably contain the Mn of 10-90mol% and the Co of 10-90mol%, especially preferably contain the Mn of 25-75mol% and the Co of 25-75mol%.If also added other element as stated, the content summation of then Mn and Co, or Mn, Co and Mo might not be 100% at this.Preferably add one or more other metal component of 0.2-50%.Particularly preferably contain 10-90mol%Mn, 10-90mol%Co and 0-10mol% molybdenum.The utmost point particularly preferably contains 25-75mol%Mn, 25-75mol%Co and 0-25mol% molybdenum.
The similar catalyst of weight content of preferred especially Mn and Co.Preferably the ratio of Mn/Co is 2: 1-1: 2, and particularly preferably be 1.5: 1 to 1: 1.5.
Catalyst according to the invention can prepare in every way.Can conceivablely have be deposited on the carrier material, the impregnated carrier material, at co-precipitation catalytic active substance under the situation that has carrier to exist, with carrier material co-precipitation catalytically-active metals compound or with the inert component co-precipitation catalytically-active metals compound that in further catalyst treatment step, forms carrier material.
Can adopt various starting compounds, as long as they can be dissolved in used solvent or can also coprecipitation under the situation of deposition or co-precipitation.The example of these starting compounds has acetate, nitrate, chloride and other soluble compound.Deposition can be through for example changing temperature, concentration (also can pass through evaporating solvent), or changing pH and/or realize through the combination of adding precipitating reagent or above means.Preferred light alcohol of solvent and/or water.Preferred especially water-based synthetic route.
Component for example through add ammonium carbonate, ammonium hydroxide, urea and alkali carbonate and hydroxide particularly from the aqueous solution co-precipitation be favourable, also be preferred therefore.Deposition can also can be carried out in batches continuously.For improving the deposition characteristic and prepared solid being carried out surface modification, also can add surface reactive material (for example ion or nonionic surface active agent or carboxylic acid).The catalyst that obtains with solid form can be known by one of skill in the art method as filter, centrifugation, evaporation and concentrating separate from material solution.Preferred centrifugation and filtration.The gained solid can further wash or also can directly further use with the form that is obtained.For improving the operability of gained catalyst, can be dried.As known for heterogeneous catalysis, it is useful that catalyst is done further arrangement.This arrangement can be calcining and heat treatment and with atmosphere reactive or for example steam treatment to improve with catalysis characteristics.Preferably hot preliminary treatment in oxidizing atmosphere under the temperature between 300 ℃-900 ℃.Can moulding and/or classification before or after said arrangement.In some cases, with active gases H for example 2, hydrocarbon, CO or said gas mixture the catalyst that will be used for commercial Application is carried out preliminary treatment possibly be useful.By means of this preliminary treatment, can change the oxidation state of existing metallic compound, perhaps influence the form of catalyst structure.
Preferably directly use this catalyst, reduce preliminary treatment or change into corresponding carbide with catalytic active substance is all or part of.
Can in various types of reactors, carry out according to technology of the present invention.Its example has fixed bed reactors, tubular reactor, rotary tube reactor, moving-burden bed reactor, has the reactor of the bubbling, turbulent flow or the ejection-type fluid bed that are known as interior circulation or external circulation fluidized bed.Also can said catalyst be introduced and for example belong to the above-mentioned type and be equipped with in the reactor of particle.These particles can be inert particles and/or can all or part ofly be made up of another kind of catalytic active substance.These particles can also be the CNT aggregations.This technology can for example continuous or discontinuous carrying out, and is said continuous or discontinuously not only refer to the supply of catalyst but also refer to formed CNT removing with used catalyst.
Possible unstrpped gas is lighter hydrocarbons such as aliphatic hydrocarbon and alkene.The oxide that but also can use alcohol, carbon is CO, band or not with heteroatomic aromatic compound and functionalized hydrocarbon aldehydes or ketones for example, as long as they can decompose on catalyst particularly.Also can use the mixture of above-mentioned hydrocarbon.The compound that is fit to is the for example oxide or the alcohol of methane, ethane, propane, butane or more senior aliphatic hydrocarbon, ethene, propylene, butylene, butadiene or more senior alkene or aromatic hydrocarbon or carbon or have heteroatomic hydrocarbon particularly.Preferably adopt short chain or medium chain promptly to have respectively from aliphatic hydrocarbon or the alkene of 1 or 2 to 10 C, perhaps list or di-aromatics.Particularly preferably adopt aliphatic hydrocarbon (C with x C xH 2x+2) and alkene (C xH y), wherein the value of x is respectively x=1-4 or 2-4.
Carbon release property raw material can be imported with gaseous form, or in reative cell or suitable front device, evaporates.Can add hydrogen or inert gas for example rare gas or nitrogen in the unstrpped gas.Also can add inert gas or have and do not have several kinds of inert gases of hydrogen to carry out CNT made according to the method for the present invention with the mixture of any desired combination.Reacting gas preferably is made up of to establish favourable reactant partial pressure carbon carrier, hydrogen and randomly a kind of inert component.Can be added on also that the component that is inertia in the reaction is used as analyzing the internal standard compound of unstrpped gas or product gas or as the detection auxiliary agent in the technological process monitoring.
This manufacturing can surpass with pressure below atmospheric pressure under carry out.This technology can be carried out under the pressure of 0.05-200 crust, the pressure of the pressure of preferred 0.1-100 crust, preferred especially 0.2-10 crust.Temperature can change in 300 ℃ to 1600 ℃ scope.Yet temperature must be high enough to make the decomposition deposition of carbon to take place with enough speed and can not cause the significantly automatically pyrolysis of hydrocarbon in gas phase.This can cause having in the formed material amorphous carbon of not preferred high-load.Favourable temperature range is between 500-800 ℃.Preferred 550 ℃ to 750 ℃ decomposition temperature.
Catalyst can add reative cell in batches or continuously.Catalyst can be reduced before introducing the real reaction chamber as stated, perhaps add with the oxidised form of main catalytically-active metals even with the hydroxide of deposition or the form of carbonate.
The CNT of making like this allows if it is used, because the low catalyst levels in the end product just can use without preprocessing usually.Material can be randomly for example through chemolysis catalyst and carrier residue, through the amorphous carbon component of the formed minute quantity of oxidation or through in inertia or reactant gas, carrying out hot post processing by refining.Prepared CNT also can be by chemical functionalization, for example to obtain the improved associativity of matrix or to make the application of surface characteristic with target mode adaptive expectation.
Prepared CNT is suitable for the additive as polymer according to the present invention, strengthens or is used to improve electric conductivity especially for machinery.The CNT of manufacturing can be used as gas and energy storage material in addition, is used for dyeing and is used as fire retardant.Because its good electrical conductivity, the CNT of manufacturing can be used as electrode material or be used to make strip conductor and conductive structure according to the present invention.Also the CNT based on manufacturing of the present invention can be used as the transmitter in the display.Preferably; This CNT is used to polymer composites, pottery or metallic composite to improve its conduction or thermal conductivity and mechanical performance, is used to make conductive coating and composite, as dyestuff; Be used for battery, capacitor, display (for example flat-panel screens) or lamp; As field-effect transistor, as the storage medium of for example hydrogen or lithium, be used in the film that for example is used for Purge gas, as catalyst or as the for example carrier material of the catalytic active component of chemical reaction; Be used for fuel cell; Be used in medical domain for example as the matrix of control cell tissue growth, be used for diagnostics and for example be used as label and be used for chemistry and physical analysis (for example being used for scanning force microscopy).
Below by some embodiment to describing with catalyst according to the invention according to the method for the invention, but these embodiment should not be understood that it is the restriction to inventive concept.
The embodiment of the invention
Embodiment 1:Prepare catalyst with different stoichiometries, solvent, precipitating reagent, temperature
Preferably through the prepared by co-precipitation catalyst.
Catalyst 1 (MCN0062_23Mn_27Co_11Mo_39Al): by the 2.5g (NH in the 50ml deionized water 4) 6Mo 7O 244H 2O, the 17.8gCo (NO in the 50ml deionized water 3) 26H 2O and the 15.4gMn (NO in the 50ml deionized water 3) 24H 2O prepares three kinds of solution.At room temperature mix said solution and stirred 5 minutes.With non-turbid mixture that is obtained and 50.0g Al (NO 3) 39H 2The solution of O in 35ml water mixes and stirs.Through dripping rare HNO 3The dissolving suspension.Below thus obtained solution is called solution A.Through with 70.0g (NH 4) 2CO 3Stir and add the solution that is called solution B in the 225ml deionized water below the preparation.Under strong agitation, room temperature is added drop-wise to two kinds of solution A and B in many necks round-bottomed flask that the 200ml deionized water is housed, and keeps pH=7.Be metered into (about 20 minutes) afterwards, then mixture stirred 5 minutes and leaching the gained solid again.Solid is suspended in water neutralization for twice through dispersed with stirring 5 minutes and leach.Filter cake 180 ℃ of dried overnight in air, and is calcined 4h at 400 ℃ subsequently in air.After the calcining, obtain the 14.9g black solid.The theoretical ratio of the reactive metal that is adopted is counted Mn based on carrier material: Co: Mo: Al 2O 3=23: 7: 11: 39.
Catalyst 2 (MCN0071_20Mn_21Co_20Mo_39Al): by the 6.8g (NH in the 50ml deionized water 4) 6Mo 7O 244H 2O, the 19.8gCo (NO in the 50ml deionized water 3) 26H 2O and the 16.8gMn (NO in the 50ml deionized water 3) 24H 2O prepares three kinds of solution.At room temperature mix said solution and stirred 5 minutes.Institute is obtained non-turbid mixture and 50.0g Al (NO 3) 39H 2The solution of O in 35ml water mixes and stirs.Below thus obtained solution is called solution A.Through with 70.0g (NH 4) 2CO 3Stir and add the solution that is called solution B in the 225ml deionized water below the preparation.Under strong agitation, room temperature is added drop-wise to two kinds of solution A and B in many necks round-bottomed flask that the 200ml deionized water is housed, and keeps pH=7.Be metered into (about 20 minutes) afterwards, then mixture stirred 5 minutes and leaching the gained solid again.Solid is suspended in water neutralization for twice through dispersed with stirring 5 minutes and leach.Filter cake 180 ℃ of dried overnight in air, and is calcined 4h at 400 ℃ subsequently in air.After the calcining, obtain the 17.7g black solid.The theoretical ratio of the reactive metal that is adopted is counted Mn based on carrier material: Co: Mo: Al 2O 3=23: 7: 11: 39.
Catalyst 3 (MCN0068_5Mn_45Co_11Mo_39Al): by the 2.5g (NH in the 50ml deionized water 4) 6Mo 7O 244H 2O, the 34.5gCo (NO in the 50ml deionized water 3) 26H 2O and the 3.2g Mn (NO in the 50ml deionized water 3) 24H 2O prepares three kinds of solution.At room temperature mix said solution and stirred 5 minutes.Institute is obtained non-turbid mixture and 50.0g Al (NO 3) 39H 2The solution of O in 35ml water mixes and stirs.Below thus obtained solution is called solution A.Through with 70.0g (NH 4) 2CO 3Stir and add the solution that is called solution B in the 225ml deionized water below the preparation.Under strong agitation, room temperature is added drop-wise to two kinds of solution A and B in the three-neck flask round-bottomed flask that the 200ml deionized water is housed, and keeps pH=7.Be metered into (about 20 minutes) afterwards, then mixture stirred 5 minutes and leaching the gained solid again.Solid is suspended in water neutralization for twice through dispersed with stirring 5 minutes and leach.Filter cake 180 ℃ of dried overnight in air, and is calcined 4h at 400 ℃ subsequently in air.After the calcining, obtain the 16.8g black solid.The theoretical ratio of the reactive metal that is adopted is counted Mn based on carrier material: Co: Mo: Al 2O 3=5: 45: 11: 39.
Catalyst 4 (MCN0070_35Mn_15Co_11Mo_39Al): by the 2.5g (NH in the 50ml deionized water 4) 6Mo 7O 244H 2O, the 11gCo (NO in the 100ml deionized water 3) 26H 2O and the 24g Mn (NO in the 10ml deionized water 3) 24H 2O prepares three kinds of solution.At room temperature mix said solution and stirred 5 minutes.Institute is obtained non-turbid mixture and 50.0g Al (NO 3) 39H 2The solution of O in 35ml water mixes and stirs.Below thus obtained solution is called solution A.Through with 70.0g (NH 4) 2CO 3Stir and add the solution that is called solution B in the 225ml deionized water below the preparation.Under strong agitation, room temperature is added drop-wise to two kinds of solution A and B in the three-neck flask round-bottomed flask that the 200ml deionized water is housed, and keeps pH=7.Be metered into (about 20 minutes) afterwards, then mixture stirred 5 minutes and leaching the gained solid again.Solid is suspended in water neutralization for twice through dispersed with stirring 5 minutes and leach.Filter cake 180 ℃ of dried overnight in air, and is calcined 4h at 400 ℃ subsequently in air.After the calcining, obtain the 16.8g black solid.The theoretical ratio of the reactive metal that is adopted is counted Mn based on carrier material: Co: Mo: Al 2O 3=35: 15: 11: 39.
Catalyst 5 (MCN0074_29Mn_3Co_39Al): by the 29.5g Co (NO in the 50ml deionized water 3) 26H 2O and the 25.1gMn (NO in the 50ml deionized water 3) 24H 2O prepares two kinds of solution.At room temperature mix said solution and stirred 5 minutes.Institute is obtained non-turbid mixture and 50.0g Al (NO 3) 39H 2The solution of O in 35ml water mixes and stirs.Below thus obtained solution is called solution A.Through with 70.0g (NH 4) 2CO 3Stir and add the solution that is called solution B in the 225ml deionized water below the preparation.Under strong agitation, room temperature is added drop-wise to two kinds of solution A and B in the three-neck flask round-bottomed flask that the 200ml deionized water is housed, and keeps pH=7.5.Be metered into (about 20 minutes) afterwards, then mixture stirred 5 minutes and leaching the gained solid again.Solid is suspended in water neutralization for twice through dispersed with stirring 5 minutes and leach.Filter cake 180 ℃ of dried overnight in air, and is calcined 4h at 400 ℃ subsequently in air.After the calcining, obtain the 21.8g black solid.The theoretical ratio of the reactive metal that is adopted is counted Mn based on carrier material: Co: Al 2O 3=29: 32: 39.
Catalyst 6 (MCN0072_23Mn_27Co_11Mo_39Mg): by the 2.5g (NH in the 50ml deionized water 4) 6Mo 7O 244H 2O, the 17.8gCo (NO in the 100ml deionized water 3) 26H 2O and the 15.4g Mn (NO in the 50ml deionized water 3) 24H 2O prepares three kinds of solution.At room temperature mix said solution and stirred 5 minutes.Institute is obtained non-turbid mixture and 41.0gMg (NO 3) 26H 2The solution of O in 35ml water mixes and stirs.Below thus obtained solution is called solution A.Through with 70.0g (NH 4) 2CO 3Stir and add the solution that is called solution B in the 225ml deionized water below the preparation.Under strong agitation, room temperature is added drop-wise to two kinds of solution A and B in the three-neck flask round-bottomed flask that the 200ml deionized water is housed, and keeps pH=7.Be metered into (about 20 minutes) afterwards, then mixture stirred 5 minutes and leaching the gained solid again.Solid is suspended in water neutralization for twice through dispersed with stirring 5 minutes and leach.Filter cake 180 ℃ of dried overnight in air, and is calcined 4h at 400 ℃ subsequently in air.After the calcining, obtain the 7.9g black solid.The theoretical ratio of the reactive metal that is adopted is counted Mn based on carrier material: Co: Mo: MgO=23: 27: 11: 39.
Dry and in 650 ℃ promptly corresponding to the temperature lower calcination of reaction temperature 2 hours after, make REM (SEM) photo of prepared catalyst.The REM photo shows that the product of co-precipitation is the aggregation (Fig. 1 and 2) of sphaerocrystal.After heat treatment (Fig. 3 and 4), the size of spherical primary crystallites increases with nanoscale, but the aggregate structure maintenance is similar.
Catalyst 7 (MCN0076_28Mn_33Co_39Mg): by the 21.8g Co (NO in the 50ml deionized water 3) 26H 2O and the 18.4g Mn (NO in the 50ml deionized water 3) 24H 2O prepares two kinds of solution.At room temperature mix said solution and stirred 5 minutes.Institute is obtained non-turbid mixture and 41.0g Mg (NO 3) 26H 2The solution of O in 35ml water mixes and stirs.Below thus obtained solution is called solution A.Through with 70.0g (NH 4) 2CO 3Stir and add the solution that is called solution B in the 225ml deionized water below the preparation.Under strong agitation, room temperature is added drop-wise to two kinds of solution A and B in the three-neck flask round-bottomed flask that the 200ml deionized water is housed, and keeps pH=7.Be metered into (about 20 minutes) afterwards, then mixture stirred 5 minutes and leaching the gained solid again.Solid is suspended in water neutralization for twice through dispersed with stirring 5 minutes and leach.Filter cake 180 ℃ of dried overnight in air, and is calcined 4h at 400 ℃ subsequently in air.After the calcining, obtain the 10.4g black solid.The theoretical ratio of the reactive metal that is adopted is counted Mn based on carrier material: Co: MgO=28: 33: 39.
Catalyst 8 (MCN0079_28Mn_33Co_39Mg): by the 21.8g Co (NO in the 50ml deionized water 3) 26H 2O and the 18.4g Mn (NO in the 50ml deionized water 3) 24H 2O prepares two kinds of solution.At room temperature mix said solution and stirred 5 minutes.Institute is obtained non-turbid mixture and 41.0g Mg (NO 3) 26H 2The solution of O in 35ml water mixes and stirs.Below thus obtained solution is called solution A.Through being stirred, 20.0g NaOH adds the solution that is called solution B in the 200ml deionized water below the preparation.Under strong agitation, room temperature is added drop-wise to two kinds of solution A and B in the three-neck flask round-bottomed flask that the 200ml deionized water is housed, and keeps pH=10.Be metered into (about 20 minutes) afterwards, then mixture stirred 5 minutes and leaching the gained solid again.Solid is suspended in water neutralization for twice through dispersed with stirring 5 minutes and leach.Filter cake 180 ℃ of dried overnight in air, and is calcined 4h at 400 ℃ subsequently in air.After the calcining, obtain the 16.8g black solid.The theoretical ratio of the reactive metal that is adopted is counted Mn based on carrier material: Co: MgO=28: 33: 39.
Embodiment 2:Carbon nano-tube, fixed bed, laboratory
Catalyst is tested in fixed bed device with laboratory scale.For this reason, at first the catalyst of ormal weight being introduced internal diameter is that 9mm also passes through heat-conducting medium from the quartz ampoule of external heat.Regulate the temperature of Solid Bed through the PID of electrical heating heat-conducting medium.By the thermocouple measurement catalyst bed or the temperature of catalyst/nanotube mixture that are contained in the inertia quartz capillary.Through electronically controlled mass flow controller with unstrpped gas and inert diluent gas input reactor.Heatable catalyst sample in hydrogen and inert gas flow at first.Reach after the requirement temperature, connect unstrpped gas.The volume ratio of raw gas mixture is ethene: H 2: Ar=45: 60: 5.Total volumetric flow rate is adjusted to 110ml NMin -1To the time of catalyst supply unstrpped gas, usually until the catalyst complete deactivation with 100-120 minute.Afterwards, measure the carbon amount of deposition through weighing.Structure and form by means of REM and the definite carbon that is deposited of tem analysis.The carbon amount based on the catalyst system therefor meter that is deposited below is called productive rate, based on calcining (m Kat, 0) afterwards catalyst weight with the reaction after weightening finish (m Always-m Kat, 0) be defined as: productive rate=(m Always-m Kat, 0)/m Kat, 0Explain that embodiments of the invention are following.Can find out that the catalyst based on the Mn-Co-Mo compound can give high yield.
Accompanying drawing:
Fig. 1 is that catalyst 6 is the REM photo of MCN0072;
Fig. 2 is that catalyst 6 is the REM photo of MCN0072;
Fig. 3 is that catalyst 6 is the REM photo of MCN0072 after 650 ℃ of calcining 2h;
Fig. 4 is that catalyst 6 is the REM photo of MCN0072 after 650 ℃ of calcining 2h;
Figure S05846507X20070716D000141
Figure S05846507X20070716D000151
Embodiment 3:The comparative example of preparation catalyst
Catalyst 9 (MCN0063_52Co_9Mo_39Al): by the 2.5g (NH in the 50ml deionized water 4) 6Mo 7O 244H 2O and the 36g Co (NO in the 50ml deionized water 3) 26H 2O prepares two kinds of solution.At room temperature mix said solution and stirred 5 minutes.Institute is obtained non-turbid mixture and 50.0g Al (NO 3) 39H 2The solution of O in 35ml water mixes and stirs.Through dripping rare HNO 3The dissolving suspension.Below thus obtained solution is called solution A.Through with 70.0g (NH 4) 2CO 3Stir and add the solution that is called solution B in the 225ml deionized water below the preparation.Under strong agitation, room temperature is added drop-wise to two kinds of solution A and B in many necks round-bottomed flask that the 200ml deionized water is housed, and keeps pH=6.Be metered into (about 20 minutes) afterwards, then mixture stirred 5 minutes and leaching the gained solid again.Solid is suspended in water neutralization for twice through dispersed with stirring 5 minutes and leach.Filter cake 180 ℃ of dried overnight in air, and is calcined 4h at 400 ℃ subsequently in air.After the calcining, obtain the 12.3g black solid.The theoretical ratio of the reactive metal that is adopted is counted Co based on carrier material: Mo: Al 2O 3=52: 9: 39.
Catalyst 10 (MCN0064_40Fe_20Co40Al): by the 40gFe (NO in the 40ml deionized water 3) 39H 2O and the 13g Co (NO in the 40ml deionized water 3) 26H 2O prepares two kinds of solution.At room temperature mix said solution and stirred 5 minutes.Institute is obtained non-turbid mixture and 50.0g Al (NO 3) 39H 2The solution of O in 35ml water mixes and stirs.Through dripping rare HNO 3The dissolving suspension.Below thus obtained solution is called solution A.Through with 70.0g (NH 4) 2CO 3Stir and add the solution that is called solution B in the 225ml deionized water below the preparation.Under strong agitation, room temperature is added drop-wise to two kinds of solution A and B in the three-neck flask round-bottomed flask that the 200ml deionized water is housed, and keeps pH=6.Be metered into (about 20 minutes) afterwards, then mixture stirred 5 minutes and leaching the gained solid again.Solid is suspended in water neutralization for twice through dispersed with stirring 5 minutes and leach.Filter cake 180 ℃ of dried overnight in air, and is calcined 4h at 400 ℃ subsequently in air.After the calcining, obtain the 16.8g black solid.The theoretical ratio of the reactive metal that is adopted is counted Fe based on carrier material: Co: Al 2O 3=40: 20: 40.
Catalyst 11 (MCN0038_13Fe_4Mo_Pural MG70): 100g is suspended in the 1500ml deionized water from the Pural MG70 of Sasol company, at 75 ℃ of stirred suspension 2h and make its cooling.Utilize (NH 4) CO 3Solution is adjusted to 9.4 with pH.By the 7.3g (NH in the 40ml deionized water 4) 6Mo 7O 244H 2O and the 94gFe (NO in the 135ml deionized water 3) 39H 2O prepares two kinds of solution.At room temperature mix said solution and stirred 5 minutes, slowly be added drop-wise to then in the Pural suspension, during pH is not dropped to below 8.95.Be metered into and carry out 2h, then mixture is further stirred 1h.Below thus obtained suspension is called suspending liquid A.Through with 400.0g (NH 4) 2CO 3Stir and add the solution that is called solution B in the 1200ml deionized water below the preparation.Under strong agitation, room temperature adds suspending liquid A with solution B.After being metered into, then mixture was stirred 5 minutes and leached the gained solid again.The ammonium acetate solution of each 1N with 2.5 liters washes solid twice.Filter cake 160 ℃ of dried overnight in air, and is calcined 4h at 400 ℃ subsequently in air.After the calcining, obtain 107.9g blush solid.Theoretical ratio based on used metallic element meter is Fe: Mo=13: 4.
Catalyst 12 (MCN0022_40Fe_60Al): by the 34.4gFe (NO in the 350ml deionized water 3) 39H 2O and 99.3g Al (NO 3) 39H 2O prepares a kind of solution.At room temperature stirred said solution 5 minutes.Through dripping rare HNO 3The dissolving suspension.Below thus obtained solution is called solution A.Through with 63.6g Na 2CO 3Stir and add the solution that is called solution B in the 600ml deionized water below the preparation.Under strong agitation, room temperature is added drop-wise to two kinds of solution A and B in many necks round-bottomed flask that the 200ml deionized water is housed, and keeps pH=7.6.Be metered into (about 60 minutes) afterwards, then mixture stirred 60 minutes and leaching the gained solid again.Wash solids twice at 80 ℃ of waters.Filter cake 80 ℃ of dried overnight in air, and is calcined 5h at 450 ℃ subsequently in air.After the calcining, obtain the 20g black solid.The theoretical ratio of the reactive metal that is adopted is counted Fe based on carrier material: Co: Al 2O 3=40: 20: 40.
Catalyst 13 (MCN0037_50Fe_11Mo_39Al): by the 12.5g (NH in the 250ml deionized water 4) 6Mo 7O 244H 2O and the 245gFe (NO in the 250ml deionized water 3) 39H 2O prepares two kinds of solution.At room temperature mixing said solution also at room temperature stirred 5 minutes.Institute is obtained non-turbid mixture and 245g Al (NO 3) 39H 2The solution of O in 163ml water mixes and stirs.Through dripping rare HNO 3The dissolving suspension.Below thus obtained solution is called solution A.Through with 350.0g (NH 4) 2CO 3Stir and add the solution that is called solution B in the 1050ml deionized water below the preparation.Under strong agitation, room temperature is added drop-wise to two kinds of solution A and B in many necks round-bottomed flask that the 1000ml deionized water is housed, and keeps pH=6.Be metered into (about 90 minutes) afterwards, then mixture stirred 5 minutes and leaching the gained solid again.Solid is suspended in water neutralization for twice through dispersed with stirring 5 minutes and leach.Filter cake 180 ℃ of dried overnight in air, and is calcined 4h at 400 ℃ subsequently in air.After the calcining, obtain the 99.3g black solid.The theoretical ratio of the reactive metal that is adopted is counted Fe based on carrier material: Mo: Al 2O 3=50: 11: 39.
Catalyst 14 (at the MCN0044_8Fe_1Mo_1Co on the Pural MG30): by the 0.1g (NH in the 5.5ml deionized water 4) 6Mo 7O 244H 2O and the 4gFe (NO in 10 ml deionized water 3) 39H 2O and 0.275g Co (NO 3) 26H 2O prepares two kinds of solution.At room temperature mixing said solution also at room temperature stirred 5 minutes.With 1/3rd the non-turbid solution that obtains to be applied to 20g through initial wetting dry in advance on the Pural MG30 of 4h at 180 ℃.Be 120 ℃ of dry 2h and subsequently 450 ℃ in air the calcining 3h after, twice similarly dipping, drying and calcining step apply remaining metal ion solution with other.The theoretical ratio of the reactive metal that is adopted is counted Fe based on carrier material: Mo: Co: Al 2O 3=8: 1: 1: 90.
Embodiment 4The comparative example of detecting catalyst in fixed bed
In laboratory installation, test equally described in catalyst that embodiment 3 is obtained such as the embodiment 2.The CNT productive rate of realizing is summarised in the table 2.Under conditions of similarity or through the productive rate that precipitates prepared catalyst, be starkly lower than the productive rate described in the embodiment 2.

Claims (4)

1. one kind prepares the method that full diameter is the CNT of 3-150nm through on heterogeneous catalysis, decomposing gaseous hydrocarbon, it is characterized in that said catalyst comprises carrier material and counts the Mn of 2-98mol%, the Co of 2-98mol% and optional Mo based on the active component content of metallic forms.
2. according to the method for claim 1, be characterised in that separately or use lighter hydrocarbons as raw material with form of mixtures.
3. according to the method for claim 1 or 2, be characterised in that this method is continuous or discontinuous carrying out, said continuous or discontinuously not only refer to the supply of catalyst but also refer to removing of formed CNT and used catalyst.
4. according to each method among the claim 1-3, be characterised in that said catalyst introduces in the reative cell with the oxidised form of main catalytically-active metals, the form of partly or entirely reduction, the hydroxide form or the carbonate form of deposition.
CN200580046507XA 2004-11-13 2005-11-08 Catalyst for producing carbon nanotubes by decomposing gaseous carbon compounds on heterogeneous catalysts Expired - Fee Related CN101142020B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102004054959A DE102004054959A1 (en) 2004-11-13 2004-11-13 Catalyst for producing carbon nanotubes by decomposition of gaseous carbon compounds on a heterogeneous catalyst
DE102004054959.1 2004-11-13
PCT/EP2005/011925 WO2006050903A2 (en) 2004-11-13 2005-11-08 Catalyst for producing carbon nanotubes by means of the decomposition of gaseous carbon compounds on a heterogeneous catalyst

Publications (2)

Publication Number Publication Date
CN101142020A CN101142020A (en) 2008-03-12
CN101142020B true CN101142020B (en) 2012-05-02

Family

ID=35788213

Family Applications (1)

Application Number Title Priority Date Filing Date
CN200580046507XA Expired - Fee Related CN101142020B (en) 2004-11-13 2005-11-08 Catalyst for producing carbon nanotubes by decomposing gaseous carbon compounds on heterogeneous catalysts

Country Status (8)

Country Link
US (1) US9409779B2 (en)
EP (1) EP1812159A2 (en)
JP (1) JP5702043B2 (en)
KR (1) KR101292489B1 (en)
CN (1) CN101142020B (en)
DE (1) DE102004054959A1 (en)
TW (1) TW200730245A (en)
WO (1) WO2006050903A2 (en)

Families Citing this family (80)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006007147A1 (en) * 2006-02-16 2007-08-23 Bayer Technology Services Gmbh Process for the continuous production of catalysts
DE102006035773A1 (en) 2006-08-01 2008-02-07 Bayer Technology Services Gmbh Process for the preparation of carbon nanoparticle-polymer mixtures by gas phase polymerization
JP4197729B2 (en) 2006-12-21 2008-12-17 昭和電工株式会社 Carbon fiber and catalyst for carbon fiber production
DE102007029008A1 (en) 2007-06-23 2008-12-24 Bayer Materialscience Ag Process for the preparation of a conductive polymer composite
DE102007046160A1 (en) * 2007-09-27 2009-04-02 Bayer Materialscience Ag Process for the preparation of a catalyst for the production of carbon nanotubes
DE102007058992A1 (en) 2007-12-07 2009-06-10 Bayer Materialscience Ag A method of making a conductive polycarbonate composite
DE102008004135B4 (en) 2008-01-11 2014-03-06 H.C. Starck Gmbh catalyst powder
DE102008020135A1 (en) * 2008-04-22 2009-10-29 Bayer Materialscience Ag Reaction resin based on an unsaturated polyester, free-radically curable vinyl compounds and carbon nanotubes
US8591858B2 (en) 2008-05-01 2013-11-26 Honda Motor Co., Ltd. Effect of hydrocarbon and transport gas feedstock on efficiency and quality of grown single-walled nanotubes
US9174847B2 (en) 2008-05-01 2015-11-03 Honda Motor Co., Ltd. Synthesis of high quality carbon single-walled nanotubes
JP5420982B2 (en) * 2008-06-18 2014-02-19 昭和電工株式会社 Carbon fiber and catalyst for carbon fiber production
JP5649269B2 (en) * 2008-06-18 2015-01-07 昭和電工株式会社 Carbon nanofiber, production method and use thereof
JP5566628B2 (en) 2008-06-18 2014-08-06 昭和電工株式会社 Carbon fiber manufacturing method
DE102008031579A1 (en) * 2008-07-03 2010-01-07 Bayer Materialscience Ag A highly efficient gas phase process for the modification and functionalization of carbon nanofibers with nitric acid vapor
DE102009011538A1 (en) 2009-03-03 2010-09-09 Pp-Mid Gmbh Producing conductive structures on surface of polymer molded bodies, comprises providing polymer molded body from a polymer phase containing carbon nanotubes and thermally treating a surface of the polymer molded body
DE102008061051A1 (en) 2008-12-08 2010-06-10 Pp-Mid Gmbh Producing conductive structures on surface of polymer molded bodies, comprises providing polymer molded body from a polymer phase containing carbon nanotubes and thermally treating a surface of the polymer molded body
DE102008048459A1 (en) 2008-09-23 2010-03-25 Pp-Mid Gmbh Producing conductive structures on surface of polymer molded bodies, comprises providing polymer molded body from a polymer phase containing carbon nanotubes and thermally treating a surface of the polymer molded body
EP2151830A1 (en) 2008-08-08 2010-02-10 pp-mid GmbH Polymer form body with conductive structures on the surface and method for its production
US20110134617A1 (en) * 2008-08-08 2011-06-09 Pp-Mid Gmbh Polymer molded bodies and printed circuit board arrangement and method for the production thereof
DE102008038524A1 (en) 2008-08-20 2010-02-25 Bayer Materialscience Ag Antistatic or electrically conductive polyurethanes and a process for their preparation
JP2012500458A (en) * 2008-08-20 2012-01-05 バイエル・マテリアルサイエンス・アクチェンゲゼルシャフト Method for producing a composite material containing carbon nanotubes and having reduced resistance
EP2184316B1 (en) 2008-11-06 2016-08-31 Clariant International Ltd Composition comprising propylene-olefin-copolymer waxes and carbon black
ES2365100T3 (en) * 2008-11-06 2011-09-22 Clariant Finance (Bvi) Limited PROCEDURE FOR THE PRODUCTION OF ORGANIC POLYMERIC PROFILES.
EP2184324A1 (en) 2008-11-06 2010-05-12 Clariant International Ltd. Compositions comprising propylene-olefin-copolymer waxes and carbon nanotubes
KR100976174B1 (en) * 2009-02-13 2010-08-16 금호석유화학 주식회사 A catalyst composition for the synthesis of thin multi-walled carbon nanotubes and its manufacturing method
EP2351705B1 (en) 2009-03-05 2014-04-30 Showa Denko K.K. Carbon fiber agglomerates and process for production of same
EP2228343A1 (en) 2009-03-13 2010-09-15 Bayer MaterialScience AG Water vapour assisted ozonolysis of carbon nanotubes
DE102009012673A1 (en) 2009-03-13 2010-09-16 Bayer Materialscience Ag Shaped bodies of carbon nanoparticle polymer blends with gradient properties of the electrical volume conductivity
EP2228406A1 (en) 2009-03-13 2010-09-15 Bayer MaterialScience AG Improved mechanical properties of epoxy filled with functionalized carbon nanotubes
EP2228414A1 (en) 2009-03-13 2010-09-15 Bayer MaterialScience AG UV-curable, wear resistant and antistatic coating filled with carbon nanotubes
DE102009012675A1 (en) 2009-03-13 2010-09-16 Bayer Materialscience Ag Process for dispersing graphitic nanoparticles
DE102009012674A1 (en) 2009-03-13 2010-09-16 Bayer Materialscience Ag Polyurethane compounds with carbon nanotubes
DE102009013418A1 (en) 2009-03-18 2010-09-23 Bayer Technology Services Gmbh Process for the dispersion of nanoparticles in fluid media
EP2411328B1 (en) 2009-03-26 2019-07-24 Northeastern University Carbon nanostructures from pyrolysis of organic materials
CA2758694C (en) 2009-04-17 2017-05-23 Seerstone Llc Method for producing solid carbon by reducing carbon oxides
DE102009024340A1 (en) 2009-06-09 2010-12-16 Bayer Materialscience Ag High flow polymer composition and process for its preparation
KR101089570B1 (en) * 2009-07-07 2011-12-05 금호석유화학 주식회사 Catalyst for preparing carbon nanotube by controlling the apparent density
CA2768474A1 (en) * 2009-07-17 2011-01-20 Southwest Nanotechnologies, Inc. Catalyst and methods for producing multi-wall carbon nanotubes
DE102009038464A1 (en) 2009-08-21 2011-02-24 Bayer Materialscience Ag Carbon nanotubes agglomerate
DE102009040047A1 (en) 2009-09-04 2011-03-17 Bayer Materialscience Ag Process for incorporating solids into polymers
JP5696269B2 (en) 2009-11-18 2015-04-08 コペリオン ゲーエムベーハー Method for producing composite material based on polymer and carbon nanotube, composite material produced by this method and use thereof
KR101018660B1 (en) * 2009-12-22 2011-03-04 금호석유화학 주식회사 A catalyst composition for the synthesis of multi-walled carbon nanotubes
DE102010005560A1 (en) 2010-01-22 2011-07-28 Bayer MaterialScience AG, 51373 Production of CNT
DE102010008173A1 (en) * 2010-02-16 2012-03-01 Bayer Materialscience Aktiengesellschaft Production of carbon nanotubes
WO2012075499A1 (en) 2010-12-03 2012-06-07 Northeastern University Method and device for fuel and power generation by clean combustion of organic waste material
CN103476878B (en) 2010-12-08 2015-09-16 黑达乐格瑞菲工业有限公司 Particulate material, the preparation comprising the matrix material of particulate material and application thereof
EP2500376A1 (en) 2011-03-17 2012-09-19 Basf Se Antistatic or electrically conductive polyurethanes
DE102011105760A1 (en) * 2011-06-15 2012-12-20 Cutec-Institut Gmbh Mixed oxide catalyst, and process for its preparation
KR101431953B1 (en) * 2012-01-11 2014-08-19 주식회사 엘지화학 Method for Preparing Homogeneous Supported Catalyst for CNT
KR101424910B1 (en) * 2012-01-11 2014-07-31 주식회사 엘지화학 Cnt and method for manufacturing thereof
CN104302575B (en) 2012-04-16 2017-03-22 赛尔斯通股份有限公司 Method for producing solid carbon by reducing carbon dioxide
MX354377B (en) 2012-04-16 2018-02-28 Seerstone Llc Methods for treating an offgas containing carbon oxides.
NO2749379T3 (en) 2012-04-16 2018-07-28
MX2014012548A (en) * 2012-04-16 2015-04-10 Seerstone Llc Methods and structures for reducing carbon oxides with non-ferrous catalysts.
EP2838838A4 (en) 2012-04-16 2015-10-21 Seerstone Llc Methods and systems for capturing and sequestering carbon and for reducing the mass of carbon oxides in a waste gas stream
US9896341B2 (en) 2012-04-23 2018-02-20 Seerstone Llc Methods of forming carbon nanotubes having a bimodal size distribution
US10815124B2 (en) 2012-07-12 2020-10-27 Seerstone Llc Solid carbon products comprising carbon nanotubes and methods of forming same
CN107651667A (en) 2012-07-12 2018-02-02 赛尔斯通股份有限公司 Solid carbon product comprising CNT with and forming method thereof
US9598286B2 (en) 2012-07-13 2017-03-21 Seerstone Llc Methods and systems for forming ammonia and solid carbon products
US9779845B2 (en) 2012-07-18 2017-10-03 Seerstone Llc Primary voltaic sources including nanofiber Schottky barrier arrays and methods of forming same
EP2700740A3 (en) 2012-08-24 2014-03-19 Showa Denko Kabushiki Kaisha Carbon fibers and catalyst for production of carbon fibers
MX2015006893A (en) 2012-11-29 2016-01-25 Seerstone Llc Reactors and methods for producing solid carbon materials.
WO2014151144A1 (en) 2013-03-15 2014-09-25 Seerstone Llc Carbon oxide reduction with intermetallic and carbide catalysts
WO2014151138A1 (en) 2013-03-15 2014-09-25 Seerstone Llc Reactors, systems, and methods for forming solid products
WO2014151898A1 (en) 2013-03-15 2014-09-25 Seerstone Llc Systems for producing solid carbon by reducing carbon oxides
EP3129321B1 (en) 2013-03-15 2021-09-29 Seerstone LLC Electrodes comprising nanostructured carbon
EP3114077A4 (en) 2013-03-15 2017-12-27 Seerstone LLC Methods of producing hydrogen and solid carbon
EP3003552A1 (en) 2013-05-24 2016-04-13 Hindustan Petroleum Corporation Ltd. Catalytic decomposition of lower hydrocarbons to produce carbon oxides free hydrogen and bamboo shaped carbon nanotubes
WO2014198752A1 (en) 2013-06-14 2014-12-18 Basf Se Heatable molded articles made from electrically conductive thermoplastic polyurethane
DE102013214229A1 (en) 2013-07-19 2015-01-22 Bayer Materialscience Ag Process for the preparation of an efficient catalyst for the production of multi-walled carbon nanotubes, multi-walled carbon nanotubes and carbon nanotube powders
JP6237225B2 (en) * 2013-12-26 2017-11-29 東洋インキScホールディングス株式会社 Catalyst for carbon nanotube synthesis
US9890045B2 (en) 2013-12-30 2018-02-13 Indian Oil Corporation Limited Process for simultaneous production of carbon nanotube and a product gas from crude oil and its products
JP6278727B2 (en) * 2014-02-04 2018-02-14 住友化学株式会社 Method for producing coprecipitate and method for producing lithium-containing composite oxide
CN103965389B (en) * 2014-05-13 2016-09-21 清华大学 The gas-phase polymerization production method of CNT-polymer composite and device
WO2018022999A1 (en) 2016-07-28 2018-02-01 Seerstone Llc. Solid carbon products comprising compressed carbon nanotubes in a container and methods of forming same
US10995000B2 (en) 2016-10-19 2021-05-04 Vanderbilt University Nanostructured carbon materials and methods of making and use thereof
CN107134579B (en) * 2017-04-17 2020-03-17 中山市卡耐特塑料有限公司 Preparation method of carbon material for positive electrode conductive agent
US10759663B2 (en) 2017-05-23 2020-09-01 Indian Oil Corporation Limited Multi-metal catalyst composition for production of morphology controlled CNT's and process thereof
KR102303667B1 (en) * 2017-10-31 2021-09-16 에스케이이노베이션 주식회사 Catalyst for synthesizing carbon nanotube and method of preparing carbon nanotube
US11181043B2 (en) 2019-09-30 2021-11-23 General Electric Company Apparatuses and methods for generating carbon particles and exhaust gas used by gas turbine systems

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3701822A (en) * 1970-06-11 1972-10-31 Chemical Construction Corp Process and catalyst for treating combustion exhaust gas
US20030148097A1 (en) * 2002-01-08 2003-08-07 Futaba Corporation Method for preparing nano-carbon fiber and nano-carbon fiber

Family Cites Families (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4058571A (en) * 1973-03-24 1977-11-15 Bayer Aktiengesellschaft Continuous process for the production of d,l'menthol
JPS5946133A (en) 1982-09-06 1984-03-15 Yoshinobu Takegami Catalyst for preparing high calorie gas, preparation thereof and preparation of high calorie gas
JPH04323101A (en) * 1991-04-23 1992-11-12 Hitachi Ltd Garbage container with deodorizing device
JPH06129613A (en) * 1992-10-20 1994-05-13 Matsushita Electric Ind Co Ltd Catalyst combustion device
CA2224690C (en) 1995-06-16 2007-06-05 Shell Canada Limited Catalyst and process for the preparation of hydrocarbons
CA2350099C (en) * 1998-11-03 2008-05-20 William Marsh Rice University Gas-phase nucleation and growth of single-wall carbon nanotubes from high pressure co
EP1054036A1 (en) * 1999-05-18 2000-11-22 Fina Research S.A. Reinforced polymers
US20030091496A1 (en) * 2001-07-23 2003-05-15 Resasco Daniel E. Method and catalyst for producing single walled carbon nanotubes
JP3912583B2 (en) * 2001-03-14 2007-05-09 三菱瓦斯化学株式会社 Method for producing oriented carbon nanotube film
AUPR421701A0 (en) * 2001-04-04 2001-05-17 Commonwealth Scientific And Industrial Research Organisation Process and apparatus for the production of carbon nanotubes
CN1141250C (en) * 2001-05-25 2004-03-10 清华大学 Process and reactor for continuously preparing nm carbon tubes with fluidized bed
JP2003012939A (en) * 2001-07-03 2003-01-15 Toray Ind Inc Carbon-containing resin composition, molding material and molded product
JP3782993B2 (en) 2001-11-28 2006-06-07 国立大学法人名古屋大学 Manufacturing method of hollow nanofiber
US6846345B1 (en) 2001-12-10 2005-01-25 The United States Of America As Represented By The Secretary Of The Navy Synthesis of metal nanoparticle compositions from metallic and ethynyl compounds
JP4020410B2 (en) * 2001-12-28 2007-12-12 大研化学工業株式会社 Catalyst for carbon material production
JP2004018290A (en) * 2002-06-13 2004-01-22 Mitsubishi Chemical Engineering Corp Granular agglomerate of carbonaceous fine fibrous body
GB0214383D0 (en) * 2002-06-21 2002-07-31 Isis Innovation Catalyst
JP3804594B2 (en) 2002-08-02 2006-08-02 日本電気株式会社 Catalyst supporting substrate, carbon nanotube growth method using the same, and transistor using carbon nanotubes
US20060008408A1 (en) * 2002-10-17 2006-01-12 Nexen Nano Tech. Co., Ltd. Fibrous nano-carbon and preparation method thereof
JP4659367B2 (en) * 2003-02-19 2011-03-30 パナソニック株式会社 Battery electrode and manufacturing method thereof
US7235159B2 (en) * 2003-09-17 2007-06-26 Molecular Nanosystems, Inc. Methods for producing and using catalytic substrates for carbon nanotube growth
CN1922347A (en) * 2003-12-15 2007-02-28 丹尼尔·E·里萨斯科 Rhenium catalysts and methods for production of single-walled carbon nanotubes
US20060078489A1 (en) * 2004-09-09 2006-04-13 Avetik Harutyunyan Synthesis of small and narrow diameter distributed carbon single walled nanotubes
AU2008337780B9 (en) * 2007-11-27 2011-09-15 Shell Internationale Research Maatschappij B.V. Catalyst with support structure

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3701822A (en) * 1970-06-11 1972-10-31 Chemical Construction Corp Process and catalyst for treating combustion exhaust gas
US20030148097A1 (en) * 2002-01-08 2003-08-07 Futaba Corporation Method for preparing nano-carbon fiber and nano-carbon fiber

Also Published As

Publication number Publication date
JP2008519679A (en) 2008-06-12
EP1812159A2 (en) 2007-08-01
WO2006050903A2 (en) 2006-05-18
CN101142020A (en) 2008-03-12
US20090140215A1 (en) 2009-06-04
TW200730245A (en) 2007-08-16
WO2006050903A3 (en) 2006-09-08
DE102004054959A1 (en) 2006-05-18
US9409779B2 (en) 2016-08-09
JP5702043B2 (en) 2015-04-15
KR20070084180A (en) 2007-08-24
KR101292489B1 (en) 2013-08-01

Similar Documents

Publication Publication Date Title
CN101142020B (en) Catalyst for producing carbon nanotubes by decomposing gaseous carbon compounds on heterogeneous catalysts
US8093176B2 (en) Process for the continuous production of catalysts
KR101446116B1 (en) Metal catalyst for producing carbon nanotubes and method for preparing carbon nanotubes using thereof
US8398949B2 (en) Carbon nanotube powder, carbon nanotubes, and processes for their production
JP4979705B2 (en) Catalyst system for multi-walled carbon nanotube manufacturing process
US8496904B2 (en) Single-walled carbon nanotube catalysts and method for preparing same
JP6449251B2 (en) Catalytic degradation of lower hydrocarbons to produce carbon oxide free hydrogen and bamboo structure carbon nanotubes
Tran et al. Carbon nanotubes synthesis by the ethylene chemical catalytic vapour deposition (CCVD) process on Fe, Co, and Fe–Co/Al2O3 sol–gel catalysts
CN104870363A (en) Carbon nanotube having high specific surface area and method for manufacturing same
CN105451883A (en) Method for producing an efficient catalyst for generating multi-walled carbon nanotubes, multi-walled carbon nanotubes and carbon nanotube powder
CN104619414A (en) Catalyst composition for the synthesis of multi-walled carbon nanotube
KR20100100890A (en) Method for producing nitrogen-doped carbon nanotubes
CN101804355A (en) Catalyst composition for the synthesis of thin multi-walled carbon nanotube and its manufacturing method
KR20100059913A (en) Method for the production of a catalyst used for manufacturing carbon nanotubes
WO2004035882A2 (en) Ultra-fine fibrous carbon and preparation method thereof
JP2020534152A (en) Catalysts and processes for adjustable root growth multi-walled carbon nanotubes
Allaedini et al. Bulk production of bamboo-shaped multi-walled carbon nanotubes via catalytic decomposition of methane over tri-metallic Ni–Co–Fe catalyst
Jiménez et al. Pilot plant scale study of the influence of the operating conditions in the production of carbon nanofibers
KR101608477B1 (en) Metal catalyst for producing carbon nanotubes and method for preparing carbon nanotubes using thereof
KR20230017835A (en) An improved catalyst for MWCNT production

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
REG Reference to a national code

Ref country code: HK

Ref legal event code: DE

Ref document number: 1118248

Country of ref document: HK

C14 Grant of patent or utility model
GR01 Patent grant
REG Reference to a national code

Ref country code: HK

Ref legal event code: WD

Ref document number: 1118248

Country of ref document: HK

C41 Transfer of patent application or patent right or utility model
TR01 Transfer of patent right

Effective date of registration: 20160613

Address after: Leverkusen, Germany

Patentee after: COVESTRO DEUTSCHLAND AG

Address before: German Monheim

Patentee before: BAYER INTELLECTUAL PROPERTY GmbH

Effective date of registration: 20160613

Address after: German Monheim

Patentee after: BAYER INTELLECTUAL PROPERTY GmbH

Address before: Germany Leverkusen

Patentee before: BAYER MATERIALSCIENCE AG

CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20120502

Termination date: 20191108

CF01 Termination of patent right due to non-payment of annual fee